Method for preparing metal cyanide catalysts using polymerizable complexing agents

ABSTRACT

Complexes of a metal cyanide polymerization catalyst and certain monomer complexing agents provide a method whereby heterogeneous, active metal cyanide catalysts can be prepared. The catalysts are useful alkylene oxide polymerization catalysts that are easily separated from the polymerization product and recycled.

This invention relates to metal cyanide complexes. More particularly, itrelates to metal cyanide catalysts that are complexed with specificcomplexing agents, to heterogeneous metal cyanide catalysts, and tomethods for polymerizing alkylene oxides in the presence of a metalcyanide catalyst.

Polyethers are prepared in large commercial quantities through thepolymerization of alkylene oxides such as propylene oxide and ethyleneoxide. The polymerization is usually conducted in the presence of aninitiator compound and a catalyst. The initiator compound usuallydetermines the functionality (number of hydroxyl groups per molecule) ofthe polymer and in some instances incorporates some desired functionalgroups into the product. The catalyst is used to provide an economicalrate of polymerization.

Metal cyanide complexes are becoming increasingly important alkyleneoxide polymerization catalysts. These complexes are often referred to as“double metal cyanide” or “DMC” catalysts, and are the subject of anumber of patents. Those patents include, for example, U.S. Pat. Nos.3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334,3,427,335 and 5,470,813, among many others. In some instances, thesemetal cyanide complexes provide the benefit of fast polymerization ratesand narrow polydispersities. Additionally, these catalysts sometimes areassociated with the production of polyethers having very low levels ofmonofunctional, unsaturated compounds.

The most common of these metal cyanide complexes, zinchexacyano-cobaltate (together with the proper complexing agent and anamount of a poly(propylene oxide)), has the advantages of being activeand of forming polypropylene oxide) having very low unsaturation.However, the catalyst is quite difficult to remove from the productpolyether. Because of this difficulty, and because the catalyst can beused in small amounts, the usual practice is to simply leave thecatalyst in the product. However, this means that the catalyst must bereplaced. In addition, the presence of the residual catalyst in thepolyether product has been reported in the patent literature to causecertain performance problems. The reported problems include poor storagestability and, in some instances, interference with downstreamprocesses. In order to reduce catalyst expense, it would be desirable toprovide a catalyst that can be recovered easily from the productpolyether.

In one aspect, this invention is a method for preparing a metal cyanidecatalyst, comprising

-   a) treating a metal cyanide catalyst with a monomer complexing agent    that contains at least one site of polymerizable carbon-carbon    unsaturation, and-   b) subjecting said treated catalyst to conditions sufficient to    polymerize the monomer complexing agent to form an organic polymer    having the metal cyanide catalyst dispersed therein.

In a second aspect, this invention is a polymer of a monomer having atleast one site of polymerizable carbon-carbon unsaturation and aheteroatom that forms a complex with a metal cyanide catalyst, thepolymer having dispersed therein a metal cyanide catalyst that iscomplexed with said polymer.

In a third aspect, this invention is a metal cyanide catalyst that iscomplexed with a monomer having at least one site of polymerizablecarbon-carbon unsaturation and a heteroatom that forms a complex with ametal cyanide catalyst.

The complex of the invention includes a water insoluble metal cyanidecatalyst. Some metal cyanide catalysts of this general type are wellknown, and are often referred to as “double metal cyanide” or “DMC”catalysts because in most instances these complexes include twodifferent metal ions. Suitable metal cyanide catalysts can berepresented by the general formulaM_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d).nM³ _(x)A_(y),wherein M is a metal ion that forms an insoluble precipitate with theM¹(CN)_(r)(X)_(t) group;

-   M¹ and M² are transition metal ions that may be the same or    different;-   each X independently represents a group other than cyanide that    coordinates with an M¹ or M² ion;-   M³ _(x)A_(y) represents a salt of metal ion M³ and anion A, wherein    M³ is the same as or different than M;-   b and c are positive numbers that, together with d, reflect an    electrostatically neutral complex;-   d is zero or a positive number;-   x and y are numbers that reflect an electrostatically neutral salt;-   r is from 4 to 6; t is from 0 to 2; and-   n is a positive number (which may be a fraction) indicating the    relative quantity of M³ _(x)A_(y).

The X groups in any M²(X)₆ do not have to be all the same. The molarratio of c:d is advantageously from about 100:0 to about 20:80, morepreferably from about 100:0 to about 50:50, and even more preferablyfrom about 100:0 to about 80:20.

The term “metal salt” is used herein to refer to a salt of the formulaM_(x)A_(y) or M³ _(x)A_(y), where M, M³, x, A and y are as definedabove.

M and M³ are preferably metal ions selected from the group consisting ofZn⁺², Fe⁺², Co⁺², Ni⁺², Mo⁺⁴, Mo⁺⁶, Al⁺³, V⁺⁴, V⁺⁵, Sr⁺², W⁺⁴, W⁺⁶,Mn⁺², Sn⁺², Sn⁺⁴, Pb⁺², Cu⁺², La⁺² and Cr⁺³. M and M³ are morepreferably Zn⁺², Fe⁺², Co⁺², Ni⁺², La⁺³ and Cr⁺³. M is most preferablyZn⁺².

M¹ and M² are preferably Fe⁺³, Fe⁺², Co⁺³, Co⁺², Cr⁺², Cr⁺³, Mn⁺², Mn⁺³,Ir⁺³, Ni⁺², Rh⁺³, Ru⁺², V⁺⁴ and V⁺⁵. Among the foregoing, those in theplus-three oxidation state are more preferred. Co⁺³ and Fe⁺³ are evenmore preferred and Co⁺³ is most preferred. M¹ and M² may be the same ordifferent.

Preferred groups X include anions such as halide (especially chloride),hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate,isothiocyanate, C₁₋₄ carboxylate and nitrite (NO₂—), and unchargedspecies such as CO, H₂O and NO. Particularly preferred groups X are NO,NO₂— and CO.

r is preferably 5 or 6, most preferably 6 and t is preferably 0 or 1,most preferably 0. In many cases, r+t will equal six.

Suitable anions A include halides such as chloride and bromide, nitrate,sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate,isothiocyanate, perchlorate, an alkanesulfonate such asmethanesulfonate, an arylenesulfonate such as p-toluenesulfonate,trifluoromethanesulfonate (triflate) and C₁₋₄ carboxylate. In addition,the anion A may include a polymerizable species such as acrylate ormethacrylate ion. When such a polymerizable species is used, the anioncan copolymerize with the monomer complexing agent.

In this invention, a metal cyanide catalyst as just described iscomplexed with a monomer that has at least one site of polymerizablecarbon-carbon unsaturation, and at least one heteroatom-containing groupthat forms a complex with the metal cyanide catalyst. Particularlysuitable heteroatom-containing groups contain nitrogen, sulfur or oxygenatoms, especially oxygen atoms, and include, for example, amide,nitrile, sulfide, hydroxyl, aldehyde, ketone, ester and ether groups.Ester, ether and hydroxyl groups, or combinations of any two or more ofthese, are most preferred. It is even more preferred that the complexingagent contains multiple heteroatom-containing groups, especiallymultiple ether and/or alcohol groups.

“A site of polymerizable carbon-carbon unsaturation” refers to a groupcontaining at least one pair of carbon atoms which are doubly or triplybonded to each other, and which can react with other like groups to forma high molecular weight polymer. Examples of such sites includeethylenic unsaturation (of the type present in vinyl acetate, vinylalcohol and the like), acrylic or methacrylic unsaturation, alkenylgroups as are present in alkenyl aromatic monomers, and conjugateddienyl groups. In this invention, a preferred site of ethylenicunsaturation is an acrylic (H₂C═CH—X—C(O)—) or methacrylic group(H₂C═C(CH₃)—C(O)—.

Thus, one group of suitable complexing agents are vinyl monomerscontaining a nitrogen or oxygen atom, such as vinyl acetate, vinyl ethylether, vinyl 2-ethylhexanoate, vinyl isobutyl ether, vinyl methylketone, 1-vinyl-2-pyrrolidinone and the like.

A more preferred group of complexing agents include acrylamide,methacrylamide and their derivatives. Examples of such derivativesinclude N,N-dialkyl acrylamides and N,N-dialkyl methacrylamides such asN,N-dimethyl acrylamide N-isobutoxymethylacrylamide and N,N-dimethylmethacrylamide.

Even more preferably, the complexing agent is an acrylic or methacrylicester, particularly having one or more ether and/or alcohol groups inthe ester portion of the molecule. These complexing agents can berepresented by the general structureR¹[—O—C(O)—CR═CH₂]_(x)where R is hydrogen or methyl, x is a number that is at least 1,preferably from 1 to 8 and more preferably from 1 to about 3, and R¹ isa hydrocarbyl group (i.e., consists of only carbon and hydrogen atoms),or a substituted hydrocarbyl group that contains one or more heteroatomsthat can complex with the metal cyanide catalyst, as described before.The group R¹ is preferably substituted with one or more ether orhydroxyl groups, or both, and may have a weight of from about 31 toabout 3000 daltons or more, preferably from about 31 to about 1200daltons.

Examples of suitable types of R¹ groups include (1) residues ofcompounds having from 1–8 (preferably 1–3) aliphatic hydroxyl groups and(2) residues of phenols or bisphenols. Compounds of the type (1) include(a) polyols such as propylene glycol, ethylene glycol,trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine,dipropylene glycol and (b) poly(oxyalkylene) compounds such aspoly(propylene oxide), poly(ethylene oxide), poly(propyleneoxide-co-ethylene oxide) (both block and random copolymers), andalkoxylated bisphenol A and alkoxylated bisphenol F having a weight ofabout 50 to about 3000 daltons, especially about 100–1200 daltons, and apreferred functionality of 2–6, especially 1–3, hydroxylgroups/molecule. Examples of the type (2) compounds include bisphenol Aand bisphenol F. Any of the compounds of types (1) or (2) may besubstituted with one or more hydrophobic groups, especially (a) asaturated or unsaturated straight chain hydrocarbyl group of 6–24 carbonatoms which is bonded directly or indirectly to the residue orpoly(alkylene oxide) chain or (b) an aryl or aryloxy group such as aphenoxy group.

Specific examples of monomer complexing agents include:

-   (A) esters of one or more moles of acrylic or methacrylic acid and a    mole of a polyol such as propylene glycol, ethylene glycol,    trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine,    dipropylene glycol, and diethylene glycol;-   (B) esters of acrylic or methacrylic acid and ethoxylated and/or    propoxylated derivatives of polyols such as those described in (A);-   (C) esters of acrylic or methacrylic acid and a bisphenol such as    bisphenol A, bisphenol F, an alkoxylated bisphenol A or alkoxylated    bisphenol F, such as bisphenol A diacrylate;-   (D) acrylamide or methacrylamide;-   (E) 1-vinyl pyrrolidinone;-   (F) N-substituted acrylamides, such as N,N-dimethyl acrylamide and    N-(isobutoxymethyl)acrylamide;-   (G) complex esters of one or more moles of acrylic or methacylic    acid and (a) one or more moles of a C₆–C₂₄ straight chain saturated    or unsaturated carboxylic acid and (b) a polyol such as propylene    glycol, ethylene glycol, trimethylolpropane, neopentyl glycol    pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or    an ethoxylated and/or propoxylated derivative of such a polyol; and-   (H) esters of acrylic or methacrylic acid and tetrahydrofurfural.

The complexed metal cyanide catalyst can be described as beingrepresented by the formulaM_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d).zL.nM³ _(x)A_(y)where L represents the monomer complexing agent and/or a mixture of themonomer complexing agent and another complexing agent, and z is apositive number representing the relative quantity of complexed Lmolecules. A quantity of water or additional complexing agent may alsobe bound into the complex. Among the catalysts of particular-interestare:

-   Zinc hexacyanocobaltate.zL.nZnCl₂;-   Zn[Co(CN)₅NO].zL.nZnCl₂;-   Zn_(s)[Co(CN)₆]_(o)[Fe(CN)₅NO]_(p).zL.nZnCl₂ (o, p=positive numbers,    s=1.5o+p);-   Zn_(s)[Co(CN)₆]_(o)[Co(NO₂)₆]_(p)[Fe(CN)₅NO]_(q).zL.nZnCl₂ (o, p,    q=positive numbers, s=1.5(o+p)+q);-   Zinc hexacyanocobaltate.zL.nLaCl₃;-   Zn[Co(CN)₅NO].zL.nLaCl₃;-   Zn[Co(CN)₆]_(o)[Fe(CN)₅NO]_(p).zL.nLaCl₃ (o, p=positive numbers,    s=1.5o+p);-   Zn_(s)[Co(CN)₆]_(o)[Co(NO₂)₆]_(p)[Fe(CN)₅NO]_(q).zL.nLaCl₃ (o, p,    q=positive numbers, s=1.5(o+p)+q);-   Zinc hexacyanocobaltate.zL.nCrCl³;-   Zn[Co(CN)₅NO].zL.nCrCl₃;-   Zn_(s)[Co(CN)₆]_(o)[Fe(CN)₅NO]_(p).zL.nCrCl₃ (o, p=positive numbers,    s=1.5o+p);-   Zn_(s)[Co(CN)₆]_(o)[Co(NO₂)₆]_(p)[Fe(CN)₅NO]_(q).zL.nCrCl₃ (o, p,    q=positive numbers, s=1.5(o+p)+q);-   Magnesium hexacyanocobaltate.zL.nZnCl₂;-   Mg[Co(CN)₅NO].zL.nZnCl₂;-   Mg_(s)[Co(CN)₆]_(o)[Fe(CN)₅NO]_(p).zL.nZnCl₂ (o, p=positive numbers,    s=1.5o+p);-   Mg_(s)[Co(CN)₆]_(o)[Co(NO₂)₆]_(p)[Fe(CN)₅NO]_(q).zL.nZnCl₂ (o, p,    q=positive numbers, s=1.5(o+p)+q);-   Magnesium hexacyanocobaltate.zL.nLaCl₃;-   Mg[Co(CN)₅NO].zL.nLaCl₃;-   Mg_(s)[Co(CN)₆]_(o)[Fe(CN)₅NO]_(p).zL.nLaCl₃ (o, p=positive numbers,    s=1.5o+p);-   Mg_(s)[Co(CN)₆]_(o)[Co(NO₂)₆]_(p)[Fe(CN)₅NO]_(q).zL.nLaCl₃ (o, p,    q=positive numbers, s=1.5(o+p)+q);-   Magnesium hexacyanocobaltate.zL.nCrCl₃;-   Mg[Co(CN)₅NO].zL.nCrCl₃;-   Mg_(s)[Co(CN)₆]_(o)[Fe(CN)₅NO]_(p).zL.nCrCl₃ (o, p=positive numbers,    s=1.5o+p);-   Mg_(s)[Co(CN)₆]_(o)[Co(NO₂)₆]_(p)[Fe(CN)₅NO]_(q).zL.nCrCl₃ (o, p,    q=positive numbers, s=1.5(o+p)+q);    as well as the various complexes such as are described at column 3    of U.S. Pat. No. 3,404,109, incorporated herein by reference. In any    of the foregoing, the chloride salts can be replaced by the    corresponding sulfate salts.

The metal cyanide catalyst is conveniently prepared by precipitating itfrom solutions or slurries of certain metal salts and metal cyanidecompounds. The precipitated metal cyanide catalyst is treated with thecomplexing agent simultaneously with the precipitation step, afterwards,or both.

The catalyst can be precipitated from aqueous or organic solution orslurry. It is preferred to prepare the catalyst using organic compoundsas solvents or dispersants, as described more below.

A first convenient method is to precipitate the metal cyanide catalystfrom a solution of the starting materials in an organic compound. Inthis method, a solution or dispersion of a compound is mixed with asolution or dispersion of a metal salt. The solvent or dispersantincludes an organic compound as described below. The soluble metalcyanide compound is represented by the general formulaH_(w)[M¹(CN)_(r)(X)_(t)], in which M¹, X, r and t are as describedbefore and w equals the absolute value of the valence of the[M¹(CN)_(r)(X)_(t)] group. If desired, a solution of a compound of thegeneral formula H_(w)M²(X)₆ may be included, either as part of thesoluble metal cyanide compound solution or as a separate solution.

The organic compound is one that meets several requirements. First, itdoes not react with the soluble metal cyanide compound or anyH_(w)M²(X)₆ compounds that may be present. In addition, it does notreact with the metal salt. It is not a solvent for the metal cyanidecatalyst complex that is formed in the reaction of the metal salt andthe soluble metal cyanide compound. Preferably, the organic compound isa solvent for the soluble metal cyanide compound and any H_(w)M²(X)₆compounds that may be used. When the catalyst is to be treatedsimultaneously with the precipitation step, the organic compoundpreferably is miscible with the monomer complexing agent. Even morepreferably, the organic compound is relatively low boiling or otherwiseeasily separated from the monomer complexing agent. A preferred organiccompound is methanol.

In the organic solution method just described, it is preferred tominimize or even eliminate water during formation of the DMC complex.

A solution of the metal cyanide compound in the organic compound can beprepared in several ways. In one preparation technique, an aqueoussolution of the corresponding alkali metal cyanide salt (i.e.,B_(w)[M¹(CN)_(r)(X)_(t)], where B represents an alkali metal ion) isformed. This may be done at an elevated temperature if necessary todissolve the metal cyanide salt. The aqueous solution is mixed with astoichiometric excess of a concentrated mineral acid of the form H_(d)J,where J is an anion that forms an insoluble salt with B and d is theabsolute value of the valence of J. Common mineral acids such assulfuric acid and hydrochloric acid are preferred. Sulfuric acid ispreferably used at a 75% or higher concentration. Hydrochloric acid ispreferably used at a 30% or higher concentration, preferably about a 37%concentration. The salt of B and J precipitates, leaving the desiredsoluble metal cyanide compound H_(w)[M¹(CN)_(r)(X)_(t)] in aqueoussolution. The organic compound is then added, usually with stirring,preferably at a slightly elevated temperature in order to maintain theH_(w)[M¹(CN)_(r)(X)_(t)] compound in solution. Because the salt of B andJ is usually hygroscopic, a significant portion of the water is removedfrom the solution with the salt. The salt is easily separated from thesupernatant liquid by filtration, centrifuging or other solid-liquidseparation technique. If desired, the salt may be washed with additionalquantities of the organic compound in order to recover any occludedH_(w)[M¹(CN)_(r)(X)_(t)] compound.

A second method for preparing the solution of the soluble metal cyanidecompound is to first form a slurry of the corresponding alkali metalcyanide salt (i.e., B_(w)[M¹(CN)_(r)(X)_(t)]), in a mixture of theorganic compound and a stoichiometric excess of a mineral acid,preferably hydrochloric acid. The hydrochloric acid can be supplied invarious ways, such as by adding concentrated aqueous HCl, introducinggaseous HCl into the organic compound, or by adding a solution of HCl inan appropriate solvent (such as diethyl ether or isopropanol). An alkalimetal salt of the acid forms and precipitates from the solution, leavingthe desired H_(w)[M¹(CN)_(r)(X)_(t)] compound dissolved in the organiccompound. The precipitate is separated and washed if desired, as before.

A third convenient method of preparing the solution of the soluble metalcyanide compound is by ion exchange. An aqueous solution of thecorresponding alkali metal salt (i.e., B_(w)[M¹(CN)_(r)(X)_(t)]) iseluted through a cation exchange resin or membrane which is originallyin the hydrogen (H⁺) form. Sufficient resin is used to provide an excessof H⁺ ions. Suitable ion exchange resins include commonly available, gelor macroporous, crosslinked polystyrene cation exchange resins, such asthose sold by The Dow Chemical Company under the trade names DOWEX®MSC-1, DOWEX® 50WX4, as well as AMBERLYST® 15 ion exchange resin, soldby Rohm & Haas. The column is typically eluted with water until thedesired soluble metal cyanide compound is recovered. The water isremoved from the eluent, yielding the desired soluble metal cyanidecompound as solid precipitate. This precipitate is then dissolved ordispersed in the organic compound. If desired, a small amount of watermay be left in the soluble metal cyanide compound when it is mixed withthe organic compound.

Other ion exchange methods for preparing the solution are described byF. Hein et al., Z. Anorg. Allg. Chem. 270, 45 (1952) and A. Ludi et al,Helv. Chem. Acta 50, 2035 (1967). Yet other methods are described byKlemm et al., Z. Anorg. Allg. Chem. 308, 179 (1961) and in the Handbookof Preparative Inorganic Chemistry, G. Brauer, Ed., Ferdinand EnkeVerlag, Stuttgart, 1981.

The H_(w)M²(X)₆ compound can be made in an analogous way.

The solution of the metal salt usually can be prepared by directlydissolving the metal salt into an organic compound. The organic compoundis as described above. In this solution, the organic compound ispreferably the same as used in the soluble metal cyanide compoundsolution. If a different organic compound is used, it is preferablymiscible with that used in the soluble metal cyanide compound solution.

The solutions are mixed in proportions such that an excess of the metalsalt is provided, based on the amount of soluble metal cyanide compound.Preferably about 1.5 to about 4, more preferably from about 2 to about 3moles of metal ion (M) are delivered per mole of M¹(CN)_(r)(X)_(t) ion(or combined moles of M¹(CN)_(r)(X)_(t) and M²(X)₆ ions, when M²(X)₆ions are present). It is also preferred that the mixing be done withagitation. Agitation is preferably continued for a period after themixing is completed. The metal cyanide catalyst,M_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d), precipitates and and forms afine dispersion in the organic compound.

An alternative method of precipitating the catalyst involves aprecipitation from aqueous solutions or suspensions. Aqueousprecipitation techniques are less preferred but can be used. In thismethod, a solution or suspension of a water-soluble metal cyanide saltor corresponding acid is combined with an aqueous solution of awater-soluble metal salt. The starting compounds are formed intoseparate aqueous solutions or suspensions, and those starting solutionsor suspensions are mixed to precipitate the metal cyanide catalyst.Conventional aqueous precipitation techniques such as are described inU.S. Pat. Nos. 3,404,109 and 5,712,216 are suitable.

A third method of precipitating the catalyst is to precipitate it from aslurry of an insoluble metal salt or zero valent metal particles in asolution of an acidic metal cyanide compound. The insoluble metal saltis, for example an oxide, hydroxide, bicarbonate, phosphate, hydrogenphosphate, dihydrogen phosphate, silicate, titanate or zirconate of ametal M as described before. ZnO is an especially preferred insolublemetal salt. Suitable metals are zinc (most preferred), iron, cobalt,nickel, molybdenum, aluminum, vanadium, strontium, tungsten, manganese,tin, lead, copper, lanthanum and chromium. The insoluble metal salt orzero valent metal reacts with the acidic metal cyanide compound to formthe salt of the metal and the acidic metal cyanide compound. If anexcess of the insoluble metal salt or zero valent metal is present,additional mineral acids such as H₂SO₄ may be added to react with theexcess insoluble metal salt or zero valent metal to form a soluble saltof the metal and the conjugate base of the additional mineral acid. Suchprocesses are described in U.S. provisional application 60/365,666,entitled “Method for Preparing Metal Cyanide Catalysts from InsolubleMetal Salts”, filed Mar. 19, 2002, and U.S. provisional application60/366,759, entitled “Method for Preparing Metal Cyanide Catalysts UsingZero Valent Metals”, filed Mar. 21, 2002, both incorporated herein byreference.

The metal cyanide catalyst is treated with the monomer complexing agenteither simultaneously with or after it is precipitated. To effectsimultaneous precipitation and treatment, the monomer complexing agentmay be present in one or both of the starting solutions, or may be addedseparately at the time the starting solutions are mixed or immediatelyafterward. If the monomer complexing agent is not a liquid, it can bedissolved in any suitable solvent, preferably the aforementioned organiccompound or another material that is miscible with the organic compound(or water or water-miscible solvent in the case of an aqueousprecipitation).

The metal cyanide catalyst may be treated with the monomer complexingagent after the precipitation step. This is most easily accomplished bywashing the precipitated catalyst one or more times with the monomercomplexing agent or a solution thereof. It is also possible to useincipient wetness techniques to introduce the monomer complexing agent.Suitable incipient wetness techniques are described in U.S. Pat. No.6,423,662, incorporated herein by reference.

Solvents (i.e., the organic compound and/or water) are preferablyremoved from the resulting catalyst complex. One method for doing thisis by filtering the catalyst to remove excess fluids. The filteredcatalyst complex can be washed one or more times with water, the monomercomplexing agent, another complexing agent, or combinations of these, ifdesired. Remaining quantities of water, organic compound and othervolatiles can be removed from the treated catalyst by techniques such asvacuum filtration if desired. The recovered solid catalyst complex maybe dried and ground in conventional manner.

It is more preferred to recover the catalyst in the form of a slurry inexcess complexing agent. This is most conveniently done when the monomercomplexing agent (and other complexing agents as may be present) is lessvolatile than the organic compound (or water) used to prepare thestarting solutions. In such a case, the organic compound and/or watermay be removed through atmospheric-pressure or vacuum distillationtechniques, leaving the catalyst and complexing agent(s) behind.

If the organic compound or water used to prepare the starting solutionsdoes not interfere with the subsequent polymerization of the monomercomplexing agent (or the activity of the catalyst complex), it is notnecessary to isolate the catalyst complex.

The treated catalyst complex is then formed into a polymer by subjectingit to conditions sufficient to cause the monomer complexing agent topolymerize. These conditions generally include exposing the treatedcatalyst complex to an elevated temperature, optionally in the presenceof a suitable catalyst or free radical initiator. The polymerization canbe performed simultaneously with the removal of volatiles if desired.

In cases where the monomer complexing agent polymerizes in a freeradical process, a free radical initiator is generally added prior topolymerization. This is conveniently done by adding the free radicalinitiator into one or both of the starting solutions, or by includingthe free radical initiator in the monomer complexing agent or in awashing step. Suitable free radical initiators include peroxy compoundsand azo compounds. Redox systems that include reducing agents andoxidizing agents are also useful. Among the useful initiators areorganic peroxides such as di-t-butyl peroxide, t-butylhydroperoxide,lauryl peroxide, dichlorobenzoyl peroxide, cumene hydroperoxide and thelike; hydrogen peroxide, peroxycarbonates such as diisopropylperoxydicarbonate, dicyclohexyl peroxy dicarbonate and the like,sulfonyl peroxides such as acetyl cyclohexyl sulfonyl peracetate,sulfonylhydrozides, azo compounds such as2,2′-azobis(2,4-dimethylpentanenitrile)2,2′-azobis(2-methylpropanenitrile) (AIBN),2,2′-azobis(2-methylbutanenitrile (VAZO® 67),1,1′-azobis(cyclohexanecarbonitrile) (VAZO® 88), t-butylhydroperoxide,inorganic peroxides such as ammonium peroxydisulfate, and potassiumperoxy disulfate, sodium metabisulfite/ferrous ammonium sulfate and thelike. The azo-type initiators are preferred.

The amount of initiator is selected to provide a controlled reactionthat proceeds at an economically attractive rate. The precise amountswill vary somewhat with the particular initiator, but in general about0.05 to about 5% by weight based on monomers is sufficient.

Curing conditions also generally include an elevated temperature, suchas from about 50 to about 150° C., more preferably from about 70–130° C.The temperature of polymerization, as well as the time required tocomplete the polymerization, is usually dependent on the particularinitiator system that is used, as different initiators tend to decomposeto form free radicals at different temperatures. It is preferred toconduct the curing under reduced pressures in order to remove volatilematerials from the resulting polymer.

If desired, additional monomers, i.e., those that do not complex withthe metal cyanide catalyst, may be incorporated into the catalystmixture and copolymerized with the monomer complexing agent. Suchadditional monomers may include, for example, include aliphaticconjugated dienes such as butadiene and isoprene; monovinylidenearomatic monomers such as styrene, α-methyl styrene, ar-methyl styrene,ar-(t-butyl)styrene, ar-chlorostyrene, ar-cyanostyrene, ar-bromostyrene,dibromostyrene, tribromostyrene, 2,5-dichlorostyrene, bromostyrene,fluorostyrene and trifluoromethylstyrene; α,β-ethylenically unsaturatedcarboxylic acids and esters thereof including itaconic acid, acrylicacid, methacrylic acid, and acrylic and methacrylic esters such asmethyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate,2-hydroxyethylmethacrylate, n-butyl acrylate, t-butyl acrylate, n-butylmethacrylate, t-butyl methacrylate, n-hexyl acrylate, maleic anhydrideand the like; α,β-ethylenically unsaturated nitriles and amides such asacrylonitrile, methacrylonitrile, acrylamide, methacrylamide,N,N-dimethylacrylamide, N-(dimethylaminomethyl) acrylamide and the like,vinyl esters such as vinyl acetate; vinyl ethers; vinyl ketones; vinyland vinylidene halides such as vinylidene chloride and vinyl chloride;maleimide, N-arylmaleimide, and N-alkymaleimides such as maleimide andN-ethyl maleimide, 1-vinyl-2-pyrrolidinone and vinyl pyridine. Amongthese, the monovinyl aromatic and acrylic or methacrylic esters arepreferred.

Monomers containing more than one site of polymerizable carbon-carbonunsaturation can be used if desired to form a crosslinked polymer.

The polymerization may be conducted as a suspension or emulsionpolymerization, so as to form discrete polymer particles complexed withthe metal cyanide catalyst. In such processes, the metal cyanidecatalyst complex is dispersed as droplets into a continuous phase andsubjected to conditions sufficient to effect polymerization of theunsaturated complexing agent.

The cured polymer advantageously contains from about 1, preferably fromabout 5, more preferably from about 10, especially from about 20 weightpercent, to about 75, preferably to about 65, more preferably to about50 weight percent of metal cyanide catalyst. In this context, the weightof the metal cyanide catalyst is considered to be the weight of theM_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d).nM³ _(x)A_(y) material,exclusive of any associated water or complexing agent compounds.

A supported catalyst is easily prepared by forming the polymer onto thesurface of a suitable support, or by conducting the polymerization stepin the presence of a support. Supports can be organic or, preferably,inorganic materials. Organic supports include polyacrylate or styrenecopolymer particles, especially when crosslinked. Inorganic supportsinclude, for example, oxides, carbides, nitrides or metals. Examples ofoxides are oxides of metals of groups IIA to IVA and IB to VIIIB,especially alumina and silica. Examples of carbides include siliconcarbide, boron carbide and tungsten carbide. Examples of nitridesinclude boron nitride, silicon nitride or aluminum nitride. Metalsupports include metals and metal alloys such as steel, aluminum, noblemetals, nickel, stainless steel, titanium, tantalum and canthal. Somesupports of particular interest include silica gel (especially inparticulate form, such as from about 60–200 mesh (U.S. Sieve)), silicachips (such as, e.g. from about 6 to about 200 mesh), aluminaparticulates or spheres, porous alumina spheres or particulates,polyacrylate or styrene/divinylbenzene copolymer particles, catalystsubstrate spheres, and the like. Particulate supports provide theadvantages of having large surface areas and being easily separated froma polyether made using the supported catalyst. However, the support mayalso be the interior surface of a reaction vessel such as a pipe ortubular reactor, a screen, honeycomb or other structure inserted withinthe reaction vessel, or the like.

Supported catalysts according to the invention advantageously containfrom about 1, preferably from about 3, more preferably from about 5,especially from about 20 weight percent, to about 50, preferably toabout 25, more preferably to about 15 weight percent of metal cyanidecatalyst. As before, the weight of the metal cyanide catalyst isconsidered to be the weight of theM_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d). nM³ _(x)A_(y) material,exclusive of any associated water or complexing agent compounds.

The catalyst complex of the invention is used to polymerize alkyleneoxides to make polyethers. In general, the process includes mixing acatalytically effective amount of the catalyst with an alkylene oxideunder polymerization conditions, and allowing the polymerization toproceed until the supply of alkylene oxide is essentially exhausted. Theconcentration of the catalyst is selected to polymerize the alkyleneoxide at a desired rate or within a desired period of time. An amount ofpolymer or supported catalyst as described above sufficient to providefrom about 5 to about 10,000 parts by weight metal cyanide catalyst(calculated as M_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d).nM³ _(x)A_(y),exclusive of supports and any associated water or complexing agentcompounds) per million parts combined weight of alkylene oxide andinitiator and comonomers, if present. More preferred catalyst levels arefrom about 20, especially from about 30, to about 5000, more preferablyabout 1000 ppm, even more preferably about 100 ppm, on the same basis.

For making high molecular weight monofunctional polyethers, it is notnecessary to include an initiator compound. However, to controlmolecular weight, impart a desired functionality (number of hydroxylgroups/molecule) or a desired terminal functional group, an initiatorcompound as described before is preferably mixed with the catalystcomplex at the beginning of the reaction. Suitable initiator compoundsinclude monoalcohols such methanol ethanol, n-propanol, isopropanoln-butanol, isobutanol, t-butanol 1-t-butoxy-2-propanol, octanol,octadecanol, 3-butyn-1-ol, 3-butene-1-ol, propargyl alcohol,2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-butene-2-ol,3-butyn-1-ol, 3-butene-1-ol and the like. The suitable monoalcoholinitiator compounds include halogenated alcohols such as2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol,3-chloro-1-propanol, 3-bromo-1-propanol, 1,3-dichloro-2-propanol,1-chloro-2-methyl-2-propanol as well as nitroalcohols, keto-alcohols,ester-alcohols (including, for example, hydroxy-functional acrylicesters), cyanoalcohols, and other inertly substituted alcohols. Suitablepolyalcohol initiators include ethylene glycol; propylene glycol,glycerine, 1,1,1-trimethylol propane, 1,1,1-trimethylol ethane,1,2,3-trihydroxybutane, pentaerythritol xylitol, arabitol mannitol,2,5-dimethyl-3-hexyn-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol,sucrose, sorbitol, alkyl glucosides such a methyl glucoside and ethylglucoside and the like. Low molecular weight polyether polyols,particular those having an equivalent weight of about 350 or less, morepreferably about 125–250, are also useful initiator compounds.

Among the alkylene oxides that can be polymerized with the catalystcomplex of the invention are ethylene oxide, propylene oxide,1,2-butylene oxide, styrene oxide, and mixtures thereof. Variousalkylene oxides can be polymerized sequentially to make blockcopolymers. More preferably, the alkylene oxide is propylene oxide or amixture of propylene oxide and ethylene oxide and/or butylene oxide.Especially preferred are propylene oxide alone or a mixture of at least75 weight % propylene oxide and up to about 25 weight % ethylene oxide.

In addition, monomers that will copolymerize with the alkylene oxide inthe presence of the catalyst complex can be used to prepare modifiedpolyether polyols. Such comonomers include oxetanes as described in U.S.Pat. Nos. 3,278,457 and 3,404,109, and anhydrides as described in U.S.Pat. Nos. 5,145,883 and 3,538,043, which yield polyethers and polyesteror polyetherester polyols, respectively. Hydroxyalkanoates such aslactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate (and their dimers),lactones and carbon dioxide are examples of other suitable monomers thatcan be polymerized with the catalyst of the invention.

The polymerization reaction typically proceeds well at temperatures fromabout 25 to about 150° C., preferably from about 80–130° C. A convenientpolymerization technique involves mixing the catalyst complex andinitiator, and pressuring the reactor with the alkylene oxide.Polymerization proceeds after a short induction period, as indicated bya loss of pressure in the reactor. Once the polymerization has begun,additional alkylene oxide is conveniently fed to the reactor on demand,until enough alkylene oxide has been added to produce a polymer of thedesired equivalent weight.

Another convenient polymerization technique is a continuous method. Insuch continuous processes, an initiator is continuously fed into acontinuous reactor, such as a continuously stirred tank reactor (CSTR)or a tubular reactor that contains the catalyst. A feed of alkyleneoxide is introduced into the reactor and the product continuouslyremoved.

The catalyst of this invention is easily separated from the productpolyether by any convenient solid-liquid separation, including simplefiltration and centrifuging. The recovered catalyst can be re-used infurther polymerization reactions.

The recovered catalyst may be washed one or more times, preferablymultiple times, with water or preferably an organic solvent such asmethanol, and then dried prior to being re-used. If the surface of thecatalyst becomes fouled or coated with polymer, the catalyst may bewashed or treated to remove the fouling or polymer coating.

The catalyst of this invention is especially useful in making propyleneoxide homopolymers and random copolymers of propylene oxide and up toabout 15 weight percent ethylene oxide (based on all monomers). Thepolymers of particular interest have a hydroxyl equivalent weight offrom about 800, preferably from about 1000, to about 5000, preferably toabout 4000, more preferably to about 2500, and unsaturation of no morethan 0.02 meq/g, preferably no more than about 0.01 meq/g.

The product polymer may have various uses, depending on its molecularweight, equivalent weight, functionality and the presence of anyfunctional groups. Polyether polyols so made are useful as raw materialsfor making polyurethanes. Polyethers can also be used as surfactants,hydraulic fluids, as raw materials for making surfactants and asstarting materials for making aminated polyethers, among other uses.

The following examples are provided to illustrate the invention, but arenot intended to limit its scope. All parts and percentages are by weightunless otherwise indicated.

EXAMPLES 1 AND 1A

A. Preparation of Supported Catalyst 1

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (1.23 g, 9.03 mmol)and poly(propylene glycol) diacrylate (M_(n) 900, Aldrich catalog#45,502-4, PPG-900-Diacrylate, 10 g, 11.11 mmol) in methanol (30 mL,23.8 g) over a period of 13 minutes with stirring. Three ½ mL rinses ofmethanol are used to rinse the H₃Co(CN)₆ solution from its container.The resultant slurry is allowed to stir for 10 minutes. An easilystirrable slurry (57.0 g) is obtained, consisting of a finely dividedsuspension in methanol. The suspension is stripped on a rotoevaporator,beginning at 35° C. with increasing temperature to 70–75° C., at avacuum of >30 inches Hg (>101.6 kPa) vacuum until the volatiles areremoved. A semi-solid white product is obtained, which is heated at70–75° C. at >30 inches Hg (>101.6 kPa) vacuum for another two hours. Apasty solid is obtained that has an acrid odor. 75 g of methanol areadded to redisperse the solid. 2,2′-Azobisisobutyronitrile (AIBN, 0.2 g)is added at room temperature and allowed to disperse. The dispersion isthen heated at 70–75° C. with slight vacuum and a nitrogen sweep. Asmethanol distills from the dispersion, a white, rubbery residue formswhich peels away from the vessel walls. After the methanol has beendistilled off, the residue is heated at 70–75° C./>30 inches Hg (>101.6kPa) vacuum for about one hour to promote curing. A rubbery whiteproduct is obtained (11.6 g). The product is further cured in a vacuumoven for an additional hour under the same conditions, and then for 3.5hours at 90–95° C./30 inches Hg (101.6 kPa) vacuum. 11.05 g of productis obtained. This is slightly less than the theoretical yield of 11.56g.

The theoretical amount of metal catalyst contained in the product isestimated as follows. It is believed that some product losses occur, sothat the amounts shown below (and corresponding amounts in subsequentexamples) represent maximum amounts.

Amount Zn_(1.5)Co(CN)₆=3.01 mmol=0.943 g

Amount “excess” ZnCl₂=9.03–4.515 mmol=4.515 mmol=0.615 g.

Weight metal catalyst=0.943 g+0.615 g=1.560 g

Weight supported catalyst=11.05 g

% metal catalyst=14.1%

B. Preparation of Supported Catalyst 1A

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃CO(CN)₆) is added to a mixture of zinc chloride (1.23 g, 9.03 mmol)and poly(ethylene glycol) diacrylate (M_(n) 700, Aldrich catalog#45,500-8, PEG-700-Diacrylate, 10 g, 14.29 mmol) in methanol (30 mL,23.8 g) over a period of 10 minutes with stirring. Three ½ mL rinses ofmethanol are used to rinse the H₃Co(CN)₆ solution from its container.The resultant slurry is allowed to stir for another 10 minutes. 0.2 g ofAIBN is added and mixed in for 8 minutes. An easily stirrable slurry(64.8 g) is obtained, consisting of a finely divided suspension inmethanol. The suspension is rotated on a rotoevaporator, at 30–35° C.,at an initial vacuum of about 28 inches Hg (94.8 kPa) vacuum whichgradually increases to >30 inches Hg (>101.6 kPa) vacuum, until thevolatiles are removed. A semi-solid white product is obtained, which isheated at 70–75° C. at >30 inches Hg (>101.6 kPa) vacuum for 90–100minutes, and then for another 16 hours, to form 11.73 g of a rubberyproduct.

The amount of metal catalyst contained in the product is estimated as upto 13.3%, using the general method described in part A.

C. Polymerization of Propylene Oxide

Supported Catalyst 1 is evaluated by mixing 0.12 g of a 700 MWpoly(propylene oxide) triol 0.58 g propylene oxide and a measured amountof the catalyst to a sealed vial, and heating at 90° C. for 18 hourswithout stirring. The conversion of the propylene oxide is thendetermined as an indication of the activity of the catalyst. The amountof catalyst is expressed in terms of parts of catalyst per million partsof combined weight of initiator and propylene oxide charged to the vial.When approximately 1000 ppm of the metal cyanide catalyst is used (basedupon DMC complex plus excess zinc salt mass; equivalent to about 12048ppm of the supported catalyst), essentially quantitative conversion ofthe propylene oxide is seen within 21 hours.

The same results are obtained when Supported Catalyst 1A is evaluated inthe same manner.

EXAMPLE 2

A. Preparation of Supported Catalyst 2

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (1.23 g, 9.03 mmol)and trimethylolpropane propoxylate triacrylate (“TMPP-644-Triacylate”,M_(n) about 644, Aldrich catalog #40,757-7, 10 g, 15.53 mmol) inmethanol (30 mL, 23.8 g) over a period of 13 minutes with stirring.Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆ solutionfrom its container. The resultant slurry is allowed to stir for 5minutes. Azobisisobutyronitrile (AIBN, 0.2 g) is added at roomtemperature and allowed to disperse with stirring for 10 minutes. Aneasily stirrable slurry (63.7 g) is obtained, consisting of a finelydivided suspension in methanol. The suspension is stripped on arotoevaporator at 30–35° C., at an initial vacuum of about 28 inches Hg(94.8 kPa) vacuum which gradually increases to >30 inches Hg (>101.6kPa) vacuum, until the volatiles are removed. A semi-solid white productis obtained, which is heated at 70–75° C. and >30 inches Hg (>101.6 kPa)vacuum for 6.5 hours to provide 12.12 g of a rubbery product.

The amount of metal catalyst contained in the product is estimated as upto 12.9%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 2 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 3

A. Preparation of Supported Catalyst 3

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g. 4.52 mmol) and “TMPP-644-Triacrylate” (10 g,15.53 mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for5 minutes. Azobisisobutyronitrile (AIBN, 0.2 g) is added at roomtemperature and allowed to disperse with stirring for 10 minutes. Aneasily stirrable slurry (65.6 g) is obtained. The suspension is rotatedon a rotoevaporator at 30–35° C., at an initial vacuum of about 28inches Hg (94.8 kPa) vacuum which gradually increases to >30 inches Hg(>101.6 kPa) vacuum, until the volatiles are removed. A semi-solid whiteproduct is obtained, which is heated at 70–75° C. and >30 inches Hg(>101.6 kPa) vacuum for about 8 hours to provide 12.42 g of a rubberyproduct.

The amount of metal catalyst contained in the product is estimated as upto 15.1%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 3 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLES 4 AND 4A

A. Preparation of Supported Catalyst 4

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g. 4.52 mmol), AIBN (0.2 g, 1.22 mmol) and“TMPP-644-Triacrylate” (10 g, 15.53 mmol) in methanol (30 mL, 23.8 g)over a period of 10 minutes with stirring. Three ½ mL rinses of methanolare used to rinse the H₃Co(CN)₆ solution from its container. Theresultant slurry is allowed to stir for 10 minutes, and 50 g of water isadded over 3–4 minutes. An easily stirrable slurry (65.6 g) is obtained.The mixture is then evacuated and back-filled with nitrogen to removeair. The mixture is then heated slowly to 38° C., 50 g of additionalwater are added, and the mixture again evaluated/back-filled withnitrogen to remove air. The mixture is heated to 60° C. overnight. Aslight exotherm is seen. A slurry is obtained, which is vacuum filteredusing Whatman® #2 filter paper to isolate the solids. The solids arethen vacuum dried at 70–75° C. and >30 inches Hg (>101.6 kPa) vacuum forabout 16.5 hours to provide 10.821 g of a rubbery product in the form ofroughly spherical particles.

The amount of metal catalyst contained in the product is estimated as upto 17.1%, using the general method described in Example 1.

B. Preparation of Supported Catalyst 4A

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (35.48 g, 6.02 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (1.23 g, 9.04 mmol),zinc acrylate (1.87 g, 9.04 mmol), AIBN (0.2 g, 1.22 mmol) and“TMPP-644-Triacrylate” (25 g, 38.82 mmol) in methanol (59.2 g) over aperiod of 15 minutes with stirring. Three ½ mL rinses of methanol areused to rinse the H₃Co(CN)₆ solution from its container. A slightexotherm is seen. The resultant slurry is allowed to stir for 10minutes, and 250 g of water are added in 50 mL portions. The mixture isthen evacuated and back-filled with nitrogen to remove air. The mixtureis then heated slowly to 50° C. over one hour, and then to 60–64° C. forabout 4 hours. Another slight exotherm is seen. A slurry is obtained,which is cooled to room temperature and vacuum filtered using Whatman®#2 filter paper to isolate the solids. The solids are rinsed with water,then with methanol, and air dried on the filter under suction for about10 minutes. The solids are then vacuum dried at 70–75° C. and >30 inchesHg (>101.6 kPa) vacuum for about 18.5 hours to provide 26.292 g of arubbery product in the form of roughly spherical particles.

The amount of metal catalyst contained in the product is estimated as upto 14.3%, using the general method described in Example 1.

C. Polymerization of Propylene Oxide

The activity of Supported Catalysts 4 and 4A are separately evaluated inthe manner described in Example 1C, with similar results.

EXAMPLE 5

A. Preparation of Supported Catalyst 5

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g. 4.52 mmol) and pentaerythritol diacrylatemonostearate (Penta-DAMS, Aldrich catalog #44,109-0, 10 g, 15.53 mmol)in slightly warm t-butanol (50 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for10 minutes. AIBN (0.2 g) is then added at room temperature and allowedto disperse with stirring for 10 minutes. 88.2 g of a slurry areobtained. The suspension is stripped on a rotoevaporator at 30–35° C.,at an initial vacuum of about 28 inches Hg (94.8 kPa) vacuum whichgradually increases to >30 inches Hg (>101.6 kPa) vacuum, until thevolatiles are removed. A pasty white product is obtained, which isheated under >30 inches Hg (>101.6 kPa) vacuum at a temperature thatincreases from 30° C. to 75° C. Slight foaming occurs as the temperaturereaches 55° C., and the product cures rapidly with exotherm to form ahard, rubbery solid. After curing at 70–75° C. under >30 inches Hg(>101.6 kPa) vacuum for 19 hours, 12.02 grams of a hard product areobtained.

The amount of metal catalyst contained in the product is estimated as upto 15.6%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 5 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 6

A. Preparation of Supported Catalyst 6

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (1.23 g, 9.03 mmol)and trimethylolpropane ethoxylate triacrylate (“TMPE-912-Triacrylate”,M_(n) about 912, Aldrich catalog #41,219-8, 10 g, 10.96 mmol) inmethanol (30 mL, 23.8 g) over a period of 10 minutes with stirring.Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆ solutionfrom its container. The resultant slurry is allowed to stir for 5minutes. AIBN (0.2 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (65.4g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–38° C., at aninitial vacuum of about 28 inches Hg (94.8 kPa) vacuum which graduallyincreases to >30 inches Hg (>101.6 kPa) vacuum, until the volatiles areremoved. A semi-solid white product is obtained, which is heated at 50°C. and 30 inches Hg (101.6 kPa) vacuum for 40 minutes. The resultingproduct is cured at 70–75° C./>30 inches Hg (>101.6 kPa) vacuum forabout 15 hours. A hard rubbery product weighing 11.89 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.8%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 6 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 7

A. Preparation of Supported Catalyst 7

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and neopentyl glycol propoxylatediacrylate (“NGP diacrylate”, M_(n) 328, Aldrich catalog #41,214-7, 10g, 30.49 mmol) in methanol (30 mL, 23.8 g) over a period of 10 minuteswith stirring. Three ½ mL rinses of methanol are used to rinse theH₃Co(CN)₆ solution from its container. The resultant slurry is allowedto stir for 5 minutes. AIBN (0.2 g) is added at room temperature andallowed to disperse with stirring for 10 minutes. An easily stirrableslurry (62.5 g) is obtained, consisting of a finely divided suspensionin methanol. The suspension is stripped on a rotoevaporator at 30–35°C./˜28 inches Hg (˜94.8 kPa) vacuum with a nitrogen sweep until thevolatiles are removed. A pasty white product is obtained, which is curedat 50° C. and 28 inches Hg (94.8 kPa) vacuum for 30 minutes. Theresulting product is cured further at 70–75° C./>30 inches Hg (>101.6kPa) vacuum for about 15 hours. A hard rubbery product weighing 12.34grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.2%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 7 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 8

A. Preparation of Supported Catalyst 8

A 3.81 wt.-% solution of H₃Co(CN)₆ in methanol (17.22 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and neopentyl glycol ethoxylatediacrylate (“NGE diacrylate”, M_(n) 300, Aldrich catalog #41,213-9, 10g, 33.33 mmol) in methanol (30 mL, 23.8 g) over a period of 10 minuteswith stirring. Three ½ mL rinses of methanol are used to rinse theH₃Co(CN)₆ solution from its container. The resultant slurry is allowedto stir for 5 minutes. AIBN (0.2 g) is added at room temperature andallowed to disperse with stirring for 10 minutes. An easily stirrableslurry (64.1 g) is obtained, consisting of a finely divided suspensionin methanol. The suspension is stripped on a rotoevaporator at 30–35°C./˜28 inches Hg (˜94.8 kPa) vacuum with a nitrogen sweep until thevolatiles are removed. A pasty white product is obtained, which is curedat 50° C. and 28 inches Hg (94.8 kPa) vacuum for 30 minutes. Theresulting product is cured further at 70–75° C./>30 inches Hg (>101.6kPa) vacuum for about 15 hours. A hard rubbery product weighing 12.38grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.2%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 8 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 9

A. Preparation of Supported Catalyst 9

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and bisphenol-A ethoxylate diacrylate(“Bis-A-E diacrylate”, M_(n) 688, Aldrich catalog #41,210-4, 10 g, 14.53mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for7 minutes. AIBN (0.2 g) is added at room temperature and allowed todisperse with stirring for 13 minutes. An easily stirrable slurry (63.8g) is obtained, consisting of a finely divided suspension in methanol.The suspension is rotated on a rotoevaporator at 30–35° C./˜28 inches Hg(˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A pasty white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for about an hour. The resulting productis cured further at 70–75° C./>30 inches Hg (>101.6 kPa) vacuum forabout 15 hours. A hard rubbery product weighing 12.17 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.7%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 9 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 10

A Preparation of Supported Catalyst 10

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and tetrahydrofurfuryl methacrylate(“THF-methacrylate”, M_(n) 170, Aldrich catalog #40945-6, 10 g, 58.75mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for5 minutes. AIBN (0.2 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (64.3g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–35° C.˜28 inches Hg(˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A pasty white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for about an hour, then at 70–75° C. and15–20 inches Hg (50.8–67.7 kPa) vacuum for 25 minutes. The resultingproduct is cured further at 70–75° C./>30 inches Hg (>101.6 kPa) vacuumfor about 17 hours. A product weighing 12.09 grams is obtained. Theproduct is hard and brittle at room temperature but elastic and rubberywhen heated.

The amount of metal catalyst contained in the product is estimated as upto 15.6%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 10 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 11

A. Preparation of Supported Catalyst 11

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and 2-hydroxy-3-phenoxypropylacrylate (“HPP acrylate”, M_(n) 222, Aldrich catalog #40736-4, 10 g, 45mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for5 minutes. AIBN (0.2 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (66.5g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–35° C./˜28 inchesHg (˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A pasty white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for about an hour and then at 70–75° C.and 15–20 inches Hg (50.8–67.7 kPa) vacuum for 25 minutes. The pressureis then reduced to >30 inches Hg (>101.6 kPa) vacuum with slightnitrogen sweep for 19 hours. A product weighing 10.93 grams is obtained.The product is hard and brittle at room temperature but elastic andrubbery when heated, and it adheres strongly to the sides of thereaction vessel.

The amount of metal catalyst contained in the product is estimated as upto 17.2%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 11 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 12

A. Preparation of Supported Catalyst 12

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and di(ethylene glycol)-2-ethylhexylether acrylate (“DEG-EH-Acrylate”, M_(n) 272, Aldrich catalog #40754-2,10 g, 36.71 mmol) in methanol (30 mL, 23.8 g) over a period of 10minutes with stirring. Three ½ mL rinses of methanol are used to rinsethe H₃Co(CN)₆ solution from its container. The resultant slurry isallowed to stir for 5 minutes. AIBN (0.2 g) is added at room temperatureand allowed to disperse with stirring for 10 minutes. An easilystirrable slurry (64.9 g) is obtained, consisting of a finely dividedsuspension in methanol. The suspension is stripped on a rotoevaporatorat 30–38° C./˜28 inches Hg (˜94.8 kPa) vacuum with a nitrogen sweepuntil the volatiles are removed. A pasty white product is obtained,which is cured at 50° C. and 28 inches Hg (94.8 kPa) vacuum for about anhour, and then at 70–75° C. and 15–20 inches Hg (50.8–67.7 kPa) vacuumfor 25 minutes. The vacuum is then increased to >30 inches Hg (>101.6kPa) vacuum with slight nitrogen sweep for 16 hours. A hard and slightlyrubbery product weighing 11.88 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.8%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 12 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 13

A. Preparation of Supported Catalyst 13

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and glycerol dimethacrylate(technical grade (85%), M_(n) 228, Aldrich catalog #43,689-5, 10 g,43.81 mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for5 minutes. AIBN (0.1 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (66.6g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–35° C./˜28 inchesHg (˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A pasty white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for about 70 minutes and then at 70–75°C. and 15–20 inches Hg (50.8–67.7 kPa) vacuum for 25 minutes. Thepressure is then reduced to >30 inches Hg (>101.6 kPa) vacuum withslight nitrogen sweep for about 16 hours. A hard and brittle productweighing 11.82 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.9%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 13 is evaluated in the mannerdescribed in Example 1C, with a somewhat slower polymerization ratebeing observed.

EXAMPLE 14

A. Preparation of Supported Catalyst 14

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (1.23 g, 9.03 mmol),and t-butanol (20 g, 270 mmol) in methanol (20 g) over a period of 10minutes with stirring. The resultant slurry is allowed to stir for 25minutes. The reaction flask is fitted with a distillation head equippedwith a nitrogen/vacuum inlet, thermocouple probe and glass stopper. Theslurry is evacuated and backfilled with nitrogen several times, andheated in stages up to 70° C. to distill methanol. The residue isallowed to stand overnight under a nitrogen pad.

Then, 15 g of t-butanol is added, and the reaction mixture againevacuated and backfilled with nitrogen several times, followed by asecond distillation at temperatures increasing to 79° C. The mixture iscooled to 40° C. and the glass stopper replaced with a rubber septum.Glycidyl methacrylate (Aldrich catalog #14, 1230-8, 1.076 g) is addedover 5 minutes via syringe and allowed to heat at 40° C. for 10 minutes,and then an additional 3.045 g. of glycidyl methacrylate is added over10 minutes. The mixture is allowed to stir for 3 hours at 40° C., andthen 3.213 g more of glycidyl methacrylate are added. After mixing for30 minutes, the reaction temperature is increased slowly to 50° C., heldat that temperature for 75 minutes, and then increased to 65° C. andheld at that temperature overnight. The mixture is then heated to 78° C.over 3 hours and cooled to room temperature. A rubbery product with asmall amount of oily residue is obtained, from which solvents aredistilled briefly at 70–75° C./30 inches Hg (101.6 kPa) vacuum. Theproduct is then cured further in a vacuum oven at 70–75° C./>30 inchesHg (>101.6 kPa) vacuum for 25 hours to produce a somewhat hard polymer.

The amount of metal catalyst contained in the product is estimated as upto 14.9%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 14 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 15

A. Preparation of Supported Catalyst 15

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and N-(isobutoxymethyl)acrylamide(M_(n) 157, Aldrich catalog #43653-4, 10 g, 63.61 mmol) in methanol (30mL, 23.8 g) over a period of 10 minutes with stirring. Three ½ mL rinsesof methanol are used to rinse the H₃Co(CN)₆ solution from its container.The resultant slurry is allowed to stir for 5 minutes. AIBN (0.2 g) isadded at room temperature and allowed to disperse with stirring for 10minutes. An easily stirrable slurry (66.5 g) is obtained, consisting ofa finely divided suspension in methanol. The suspension is stripped on arotoevaporator at 30–35° C./˜28 inches Hg (˜94.8 kPa) vacuum with anitrogen sweep until the volatiles are removed. A pasty white product isobtained, which is cured at 50° C. and 28 inches Hg (94.8 kPa) vacuumfor about 75 minutes and then at 70–75° C./15–20 inches Hg (50.8–67.7kPa) vacuum for 25 minutes. The pressure is then reduced to >30 inchesHg (>101.6 kPa) vacuum with slight nitrogen sweep for about 18 hours. Ahard and brittle product weighing 11.57 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 16.2%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 15 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 16

A. Preparation of Supported Catalyst 16

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and acrylamide (10 g, 140.7 mmol) inmethanol (30 mL, 23.8 g) over a period of 10 minutes with stirring.Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆ solutionfrom its container. The resultant slurry is allowed to stir for 5minutes. AIBN (0.05 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (71.2g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–35° C./˜28 inchesHg (˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A solid white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for about 35 minutes. The resultingproduct is cured further at 70–75° C./22 inches Hg (74.5 kPa) vacuum for40 minutes, and then the pressure is reduced to >30 inches Hg (>101.6kPa) vacuum with slight nitrogen sweep for about 16 hours. A hard, whitefoamed product weighing 11.97 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.7%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 16 is evaluated in the mannerdescribed in Example 1C, with a somewhat slower polymerization ratebeing noted.

EXAMPLE 17

A. Preparation of Supported Catalyst 17

A 3.70 wt.-% solution of H₃Co(CN)₆ in methanol (17.74 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and N,N-dimethylacrylamide (10 g,100.9 mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for5 minutes. AIBN (0.05 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (64.4g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–35° C./˜28 inchesHg (˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A pasty white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for 70 minutes. The resulting product iscured further at 70–75° C./22 inches Hg (74.5 kPa) vacuum for 45minutes, and then the pressure is reduced to >30 inches Hg (>101.6 kPa)vacuum with slight nitrogen sweep for about 16 hours. A hard andsomewhat brittle product weighing 11.13 grams is obtained.

The amount of metal catalyst contained in the product is estimated as upto 16.9%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 17 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 18

A. Preparation of Supported Catalyst 18

A 3.84 wt.-% solution of H₃Co(CN)₆ in methanol (17.09 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol) and 1-vinyl-2-pyrrolidinone (10 g,89.98 mmol) in methanol (30 mL, 23.8 g) over a period of 10 minutes withstirring. Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆solution from its container. The resultant slurry is allowed to stir for5 minutes. AIBN (0.05 g) is added at room temperature and allowed todisperse with stirring for 10 minutes. An easily stirrable slurry (75.8g) is obtained, consisting of a finely divided suspension in methanol.The suspension is stripped on a rotoevaporator at 30–35° C./˜28 inchesHg (˜94.8 kPa) vacuum with a nitrogen sweep until the volatiles areremoved. A pasty white product is obtained, which is cured at 50° C. and28 inches Hg (94.8 kPa) vacuum for about 5–10 minutes. Because somedistillation begins to occur, the vacuum is reduced to 10–15 inches Hg(33.9–50.8 kPa) vacuum and these conditions maintained another 40minutes. The resulting product is cured further at 70–75° C./5 inches Hg(16.9 kPa) vacuum for 3 hours and then the pressure is reduced to >30inches Hg (>101.6 kPa) vacuum with slight nitrogen sweep for anadditional 105 minutes. 11.88 grams of a solid product that is somewhatpliable when warm is obtained.

The amount of metal catalyst contained in the product is estimated as upto 15.9%, using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 18 is evaluated in the mannerdescribed in Example 1C, with a somewhat slower polymerization ratebeing observed.

EXAMPLE 19

A. Preparation of Supported Catalyst 19

A 3.84 wt.-% solution of H₃Co(CN)₆ in methanol (17.09 g, 3.01 mmolH₃Co(CN)₆) is added to a mixture of zinc chloride (0.615 g, 4.52 mmol),zinc acrylate (0.937 g, 4.52 mmol), trimethylolpropane propoxylatetriacrylate (“TMPP-470-Triacrylate”, M_(n) 470, Aldrich catalog#40,756-9, 2 g, 4.26 mmol), 3-(trimethoxysilyl)propyl methacrylate (MW248, Aldrich catalog #44,015-9, 2 g, 8.05 mmol) and AIBN (0.03 g) inmethanol (20 mL, 15.8 g) over a period of 10 minutes with stirring.Three ½ mL rinses of methanol are used to rinse the H₃Co(CN)₆ solutionfrom its container. The resultant slurry is allowed to stir for 15minutes. An easily stirrable slurry (42.1 g) is obtained, consisting ofa finely divided suspension in methanol.

Silica gel (Davisil™ Grade 646, 35–60 mesh, 150 Angstrom pore size,Aldrich catalog #23,684-5, 50 g) is added to a stripping flask, and theslurry is added in small batches over 30 minutes with occasional mildagitation. The resulting mixture is dried on a rotoevaporator for 15minutes at room temperature and 20 inches Hg (67.7 kPa) vacuum with anitrogen sweep until the silica becomes free-flowing without clumps. Thevacuum is then increased to 20–25 inches Hg (67.7–84.7 kPa) vacuum foranother 15 minutes. The temperature and pressure are then increased to30–35° C. and 25–26 inches Hg (84.7–88 kPa) vacuum, and methanol beginsto distill. After 15 minutes, a white, free-flowing silica product isobtained. The temperature is then increased to 50° C. for 30 minutes,and then to 75° C. [still at 25–26 inches Hg (84.7–88 kPa) vacuum] for20 minutes. The vacuum is then increased to >30 inches Hg (>101.6 kPa)vacuum for about 15 hours. The resulting product consists of silica gelparticles having a coating that contains active catalyst. The amount ofmetal catalyst contained in the product is estimated as up to 3.52%,using the general method described in Example 1.

B. Polymerization of Propylene Oxide

The activity of Supported Catalyst 19 is evaluated in the mannerdescribed in Example 1C, with similar results.

EXAMPLE 20

A. Preparation of Methanolic H₃Co(CN)₆ Solution

K₃Co(CN)₆ (10.0 g, 30.09 mmol) is dissolved in deionized water (23.3 g)while heating to 45° C. Concentrated sulfuric acid (96%, 12.3 g, ˜120.4mmol) is added dropwise over about 10 minutes with stirring. Methanol(100 g) is added over a total of 5–10 minutes. A white precipitate formsduring the methanol addition. The slurry is then cooled to about 10° C.,and vacuum filtered to remove the precipitate. A light yellow filtrateis obtained, weighing 150.23 g and theoretically containing 4.49% byweight H₃Co(CN)₆.

B. Preparation of Supported Catalyst 20

A portion of the 4.49 wt.-% solution of H₃Co(CN)₆ in methanol from partA above (48.57 g, ˜10.0 mmol H₃Co(CN)₆) is added to a slurry of zincoxide (3.09 g, 38.0 mmol) and trimethylolpropane (2.44 g, 18.2 mmol) inmethanol (20 mL, 15.8 g) over a period of 75 minutes with rapidstirring. The resultant slurry is allowed to stir for 15 minutes. Aneasily stirrable slurry is obtained, consisting of a finely dividedsuspension in methanol, with some unreacted zinc oxide present. Thisslurry is heated at 50° C. for two hours. Poly(ethylene glycol)dimethacrylate (“PEG(200)-DMA”, 121.76 g, 368.9 mmol) and AIBN (0.109 g)are added to the slurry at 26° C., and the resulting mixture stirred for15 minutes. The slurry is gradually heated to 50° C. over about an hour.An exotherm occurs as the polymerization begins, raising the slurrytemperature to about 60–62° C. The slurry thickens, and 80 mL ofmethanol is added. The mixture is stirred for 3 hours at 60° C., andallowed to sit overnight at room temperature.

The mixture is then reheated to 60° C. for about five hours, cooled toroom temperature and vacuum filtered. The solids are washed withmethanol and air dried with suction for about one hour. The solids arethen dried in a vacuum oven at 76° C. and 26 inches Hg (84.7 kPa) vacuumwith a nitrogen sweep for 15 hours. The drying conditions are increasedto 120° C./25 inches Hg (84.7 kPa) vacuum for one hour, and furtherincreased to 150° C./30 inches Hg (101.6 kPa) vacuum for three hours.The resulting product weighs 121.23 g. The amount of metal catalystcontained in the product is estimated as up to 4.27%, using the generalmethod described in Example 1.

C. Polymerization of Propylene Oxide

The activity of Supported Catalyst 20 is evaluated in the mannerdescribed in Example 1C, with similar results.

1. A catalyst complex comprising a water insoluble metal cyanidecatalyst that is complexed with a monomer complexing agent that has atleast one polymerizable site of carbon-carbon unsaturation.
 2. Thecatalyst complex of claim 1, which is represented by the structureM_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d).zL.nM³ _(x)A_(y) wherein M is ametal ion that forms an insoluble precipitate with the M¹(CN)_(r)(X)_(t)group; M¹ and M² are transition metal ions that may be the same ordifferent; each X independently represents a group other than cyanidethat coordinates with an M¹ or M² ion; M³ _(x)A_(Y) represents salt ofmetal ion M³ and anion A, wherein M³ is the same as or different than M;b and c are positive numbers that, together with d, reflect anelectrostatically neutral complex; d is zero or a positive number; x andy are numbers that reflect an electrostatically neutral salt; r is from4 to 6; t is from 0 to 2; n is a positive number indicating the relativequantity of M³ _(x)A_(y); L represents the complexing agent and z is apositive number representing the relative quantity of complexed Lmolecules.
 3. The catalyst complex of claim 2, which is a zinchexacyanocobaltate catalyst complex wherein M³ is zinc.
 4. The catalystcomplex of claim 1, wherein the monomer complexing agent is a vinylmonomer containing a nitrogen or oxygen atom.
 5. The catalyst complex ofclaim 4, wherein the monomer complexing agent is vinyl acetate, vinylethyl ether, vinyl 2-ethylhexanoate, vinyl isobutyl ether, vinyl methylketone, 1-vinyl-2-pyrrolidinone or a mixture of two or more thereof. 6.The catalyst complex of claim 1, wherein the monomer complexing agent isacrylamide, methacrylamide, an N,N-dialkyl acrylamide or an N,N-dialkylmethacrylamide.
 7. The catalyst complex of claim 1, wherein the monomercomplexing agent is an acrylic or methacrylic ester.
 8. The catalystcomplex of claim 7, wherein the acrylic or methacrylic ester has one ormore ether and/or alcohol groups in the ester portion of the molecule.9. The catalyst complex of claim 8, wherein the acrylic or methacrylicester is represented by the structureR¹[—O—C(0)—CR═CH₂]_(x) where R is hydrogen or methyl, x is a number thatis at least 1 and R¹ is (1) the residue of a compound having from 1–8aliphatic hydroxyl groups, (2) the residue of a phenol or bisphenol. 10.The catalyst complex of claim 9, wherein the acrylic or methacrylicester is (A) an ester of one or more moles of acrylic or methacrylicacid and a mole of propylene glycol, ethylene glycol,trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine,dipropylene glycol, diethylene glycol or an ethoxylated and/orpropoxylated derivative of any of the foregoing, (B) a complex ester ofone or more moles of acrylic or methacylic acid and (a) one or moremoles of a C₆–C₂₄ straight chain saturated or unsaturated carboxylicacid and (b) propylene glycol, ethylene glycol, trimethylolpropane,neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol,diethylene glycol or an ethoxylated and/or propoxylated derivative ofany of the foregoing; or (C) a mixture of two or more of (A) and/or (B).11. A polymer having dispersed therein a metal cyanide catalyst that iscomplexed with said polymer, formed by subjecting the catalyst complexof claim 1 to conditions sufficient to polymerize the monomer complexingagent.
 12. A polymer having dispersed therein a metal cyanide catalystthat is complexed with said polymer, formed by subjecting the catalystcomplex of claim 3 to conditions sufficient to polymerize the monomercomplexing agent.
 13. A polymer having dispersed therein a metal cyanidecatalyst that is complexed with said polymer, formed by subjecting thecatalyst complex of claim 4 to conditions sufficient to polymerize themonomer complexing agent.
 14. A polymer having dispersed therein a metalcyanide catalyst that is complexed with said polymer, formed bysubjecting the catalyst complex of claim 5 to conditions sufficient topolymerize the monomer complexing agent.
 15. A polymer having dispersedtherein a metal cyanide catalyst that is complexed with said polymer,formed by subjecting the catalyst complex of claim 6 to conditionssufficient to polymerize the monomer complexing agent.
 16. A polymerhaving dispersed therein a metal cyanide catalyst that is complexed withsaid polymer, formed by subjecting the catalyst complex of claim 7 toconditions sufficient to polymerize the monomer complexing agent.
 17. Apolymer having dispersed therein a metal cyanide catalyst that iscomplexed with said polymer, formed by subjecting the catalyst complexof claim 9 to conditions sufficient to polymerize the monomer complexingagent.
 18. A polymer having dispersed therein a metal cyanide catalystthat is complexed with said polymer.
 19. The polymer of claim 18,wherein the polymer is a polymer of a vinyl monomer containing anitrogen or oxygen atom.
 20. The polymer of claim 19, wherein thepolymer is a polymer of acrylamide, methacrylamide, an N,N-dialkylacrylamide or an N,N-dialkyl methacrylamide.
 21. The polymer of claim19, wherein the polymer is a polymer of an acrylic or methacrylic ester.22. The polymer of claim 18, wherein the polymer is a polymer of (A) anester of one or more moles of acrylic or methacrylic acid and a mole ofpropylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol,pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or anethoxylated and/or propoxylated derivative of any of the foregoing, (B)a complex ester of one or more moles of acrylic or methacylic acid and(a) one or more moles of a C₆–C₂₄ straight chain saturated orunsaturated carboxylic acid and (b) propylene glycol, ethylene glycol,trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine,dipropylene glycol, diethylene glycol or an ethoxylated and/orpropoxylated derivative of any of the foregoing; or (C) a mixture of twoor more of (A) and/or (B).
 23. A method of making a polymerizationcatalyst, comprising a) treating a metal cyanide catalyst with acomplexing agent having at least one site of polymerizable carbon-carbonunsaturation, and b) subjecting said treated catalyst to conditionssufficient to polymerize said complexing agent to form a polymercontaining the metal cyanide catalyst dispersed within it.
 24. Themethod of claim 23, wherein the metal cyanide catalyst is represented bythe structureM_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d) .zL.nM³ _(x)A_(y) wherein M isa metal ion that forms an insoluble precipitate with theM¹(CN)_(r)(X)_(t) group; M¹ and M² are transition metal ions that may bethe same or different; each X independently represents a group otherthan cyanide that coordinates with an M¹ or M² ion; M³ _(x)A_(y)represents salt of metal ion M³ and anion A, wherein M³ is the same asor different than M; b and c are positive numbers that, together with d,reflect an electrostatically neutral complex; d is zero or a positivenumber; x and y are numbers that reflect an electrostatically neutralsalt; r is from 4 to 6; t is from 0 to 2; n is a positive numberindicating the relative quantity of M³ _(x)A_(y); L represents thecomplexing agent and z is a positive number representing the relativequantity of complexed L molecules.
 25. The method of claim 24, whereinthe polymerization is performed in the presence of a free radicalinitiator.
 26. The method of claim 24, wherein the metal cyanidecatalyst is precipitated from starting solutions or suspensions, andstep b) is conducted simultaneously with the precipitation of thecatalyst.
 27. The method of claim 25, wherein the free radical initiatoris an azo-type initiator.
 28. The method of claim 23, wherein themonomer complexing agent is a vinyl monomer containing a nitrogen oroxygen atom.
 29. The method of claim 23, wherein the monomer complexingagent is vinyl acetate, vinyl ethyl ether, vinyl 2-ethylhexanoate, vinylisobutyl ether, vinyl methyl ketone, 1-vinyl-2-pyrrolidinone or amixture of two or more thereof.
 30. The method of claim 23, wherein themonomer complexing agent is acrylamide, methacrylamide, an N,N-dialkylacrylamide or an N,N-dialkyl methacrylamide.
 31. The method of claim 23,wherein the monomer complexing agent is an acrylic or methacrylic ester.32. The method of claim 31, wherein the acrylic or methacrylic ester hasone or more ether and/or alcohol groups in the ester portion of themolecule.
 33. The method of claim 32, wherein the acrylic or methacrylicester is represented by the structureR¹[—O—C(O)—CR═CH₂]_(x) where R is hydrogen or methyl, x is a number thatis at least 1, and R¹ is (1) the residue of a compound having from 1–8aliphatic hydroxyl groups, (2) the residue of a phenol or bisphenol. 34.The method of claim 33, wherein the acrylic or methacrylic ester is (A)an ester of one or more moles of acrylic or methacrylic acid and a moleof propylene glycol, ethylene glycol, trimethylolpropane, neopentylglycol, pentaerythritol, glycerine, dipropylene glycol, diethyleneglycol or an ethoxylated and/or propoxylated derivative of any of theforegoing, (B) a complex ester of one or more moles of acrylic ormethacylic acid and (a) one or more moles of a C₆–C₂₄ straight chainsaturated or unsaturated carboxylic acid and (b) propylene glycol,ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol,glycerine, dipropylene glycol, diethylene glycol or an ethoxylatedand/or propoxylated derivative of any of the foregoing; or (C) a mixtureof two or more of (A) and/or (B).
 35. The method of claim 23, whereinvolatiles are stripped from the catalyst prior to polymerization of themonomer complexing agent.
 36. The method of claim 23, wherein volatilesare stripped from the catalyst simultaneously with the polymerization ofthe monomer complexing agent.
 37. The method of claim 23, wherein step bis performed in the presence of a support.
 38. The method of claim 37,wherein the support is a particulate silica, silica chips, aluminaparticulates or spheres, porous alumina spheres or particulates,polyacrylate or styrene/divinylbenzene copolymer particles or catalystsubstrate spheres.
 39. A method of making a polyether, comprisingsubjecting a mixture of an alkylene oxide and an initiator compound toconditions sufficient to polymerize the alkylene oxide while in thepresence of the polymer of claim 11.